Reactive dyestuffs



United States Patent 3,399,194 REACTIVE DYESTUFFS Angelo Mangini,Germana Mazzanti, and Antonio Tundo,

Bologna, Italy, assignors to Aziende Colori Nazionali Afiini ACNAS.p.A., Milan, Italy No Drawing. Filed Apr. 21, 1964, Ser. No. 361,553

Claims priority, application Italy, Apr. 26, 1963, 8,708/ 63; Aug. 8,1963, 16,515/ 63 2 Claims. (Cl. 260-249) ABSTRACT OF THE DISCLOSUREDyestuffs containing as the reactive group wherein R is an aliphaticgroup containing 1 to 5 carbon atoms, and R is aliphatic of 1-5 carbonatoms and H. Illustratory are dyestuffs of the formula wherein R and Rhave the above meaning, Ar is substituted or unsubstituted benzene,naphthalene or diphenyl and R is a radical of sulphonated pyrazolonederivatives, sulphonated naphthylamines, sulphonated naphthols,sulphonated amino-naphthols and anthraquinones. Process also disclosed.

Our invention relates to a new class of reactive dyestuffs and moreparticularly of dyestuffs capable of forming during dyeing chemicalbonds with the hydroxyl groups of cellulose, thereby yielding dyesparticularly resistant to laundering.

Several classes of dyestuffs having such reactive groups are known, inparticular dyestulfs including one of the following reactive groups:monochlorotriazine, dichlorotriazine, dichloropyrimidine,beta-chloropropionamine, vinylsulphone and furthermore monohalodinitro-,monohalotrinitro-, dihalodinitro-, trihalotrinitro-benzene groups.

The methods for application of these dyestuffs vary depending upon thereactivity of their reactive groups.

This invention is based on the discovery of a new class of dyestuffshaving as reactive group the radical (I) l la w 3,399,194 Patented Aug.27, 1968 derivatives having in the triazine nucleus the substitutinggroup has a higher reactivity than chlorines on triazines having othersubstituents, such as the amino group, the amino group monoordisubstituted with alkyl, aralkyl, alkylaryl, heterocyclic radicals,optionally substituted with an appropriate functional group of theorganic chemistry.

The higher reactivity exhibited by dyestulfs having as reactive groupthe radical:

N N R l laaoN wherein R and R have the above-mentioned meaning withrespect to the dyestuffs containing the reactive radical I LNHR whereinR is an alkylic or arylic residue optionally substituted, can be shown,in a preliminary way, by the fact that, while the condensation betweenan arylamine and the Compound III takes place at 58 C., the condensationbetween the Compound IV and the same arylamine takes place at atemperature of 3540 0.:

This remarkably improved reactivity with respect to the reactivetriazine dyestuifs of the known art allows the application of saiddyestuffs at a lower temperature; using a somewhat smaller amount ofalcohols (with consequent decrease of the costs) and with a greatervelocity, thus favoring the use of continuous dyeing methods. Theabovementioned advantages exist also in the textile printing procedures.

3 The reactive potentialty of cyanuric chloride is reduced by thepresence of the group wherein R and R have the above-mentioned meaningin such a measure as to reach the right degree of reactivity. It is wellknown that an excessive reactivity, like that of some dichlorotriazinedyestuffs, causes a certain instability in drying and storage. Thereceptivity of the fiber toward the dye is also increased, causing coloreffects of limited uniformity.

All the reactive dyestuffs belonging to the class of this invention dyecellulosic fibers in the presenec of electrolytes, from an alkalinebath. They diflfer from the known dyestuffs because of their particulardyeing power and of the better fastness to light. Shades particularlyfast to laundering are obtained.

The dyestuffs according to the present invention are prepared byreacting cyanuric chloride with KCN and a carbonylic compound (a ketoneor an aldehyde) having the following general formula:

CO R! in which R and R have the above-indicated meanings, andsubsequently condensing the thus obtained triazine (V) wherein Ar is adifferently substituted benzene, naphthalene, diphenyl nucleus, etc.

By diazotizing the amine (VI) and coupling with various coupling agentsthe reactive dyestuffs having the structure (VII):

N 1 01f ENE-A1 N N R By coupling said Compound VIII with the desireddiazonium salt, the reactive dyestuffs (IX):

wherein Ar is -a suitably substituted benzene, naphthalene, or diphenylnucleus, are obtained.

Triazine (V) can also be directly condensed with phthalocyanines or withsulphonated azo or anthraquinone dyestuffs containing a free amino groupto originate directly the reactive dyestuffs (X):

EXAMPLE 1 Preparation of triazine (XI):

CH3 ]CN N i (Db-L J-Ol \N (XI) 30 g. of cyanuric chloride are dissolvedin 200 cc. acetone and 50 g. of crushed ice are added to the solution.The suspension thus obtained is first neutralized with 10% Na CO andthen an aqueous solution of potassium cyanide (KCN 10.6 g.; H 0 150 cc.)is added dropwise, at 2-3 C., during about 45 minutes.

During the dropwise addition of potassium cyanide, the pH of thereaction mass is 9.5-10.

At the end of the addition of KCN (45 minutes) the pH of the suspensiongradually decreases and after further 30-40 minutes is 6.5.

The suspension is neutralized and diluted with water and ice (H 0 200cc.; ice 200 g.) and then is filtered. The precipitate is carefullywashed with water and then dried under vacuum.

The product after crystallization from n-hexane melts at -9l C.

Preparation of the amine O -CHa 0.1 mol of triazine (XI) is dissolved in50 cc. acetone and the solution is poured into cc. water and 100 g. me.In the thus obtained emulsion the aqueous neutral N I o1-L J-NH-Q-SON OH0.1 mol of amine, obtained as above described, is directly diazotizedand the diaz-onium salt thus obtained is coupled at 4-6 C. with 0.1 molof the benzoyl H acid at pH=8.5 At the end of the addition of thediazonium salt, the reaction mass is agitated for 3-4 hours, the pH isadjusted to 7.2 and the mass is salted out. The precipitate thusobtained is centrifuged and dried at 40 C. It dyes cotton in red shadefast to washing.

EXAMPLE 2 If as a coupling agent for the amine prepared according to thepreceding example instead of the sulphonated m-phenylenediamine,1-(4'-sulpho-phenyl) 3 methyl-5- pyrazolone is used, a dyestulf havingthe following structure:

is obtained; it dyes cotton in yellow, very fast to Wet treatments.

EXAMPLE 3 By coupling the amine prepared according to Example 1 with thebenzoyl-K acid, the following dyestuff:

SOaNa OH NH-C O-CsHs is obtained; it dyes cotton in a red shade, veryfast to wet treatments.

EXAMPLE 4 ,Using as coupling agent of the amine prepared according toExample 1, the 1-(2',5'-dichloro-4-sulphophenyl)-3-methyl-S-pyrazolone,the following dyestuff is obtained which dyes the cellulose fibers in ayellow shade, fast to washing.

S O3Na 7 EXAMPLE 5 By working as described in the preceding examples andusing as coupling agent the ureido of the isogamma acid, the dyestuif:

/CH3 O-CEa is obtained, which dyes cotton in a fast orange shade.

EXAMPLE 6 A dyestuff having the following structure:

CH3 OCCH3 N mi is obtained in a way similar to that used for obtainingthe preceding dyestuffs, using as coupling agent the acetylisogammaacid.

This dyestutf dyes cotton in an orange shade very fast to washing.

EXAMPLE 7 Preparation of the triazinic dyestutf having the followingstructure:

30 g. of the triazine (XI) are dissolved in 15 cc. of acetone and arepoured into 50 g. of water and ice. In the suspension kept underagitation an aqueous solution containing 1.4 g. of sodium acetate and7.3 g. of the amine dissolved in 280 cc. of water is poured dropwise.

After the addition, the temperature is allowed to reach 2025 C. and thewhole is agitated until solution is completed (46 hours). The solutionis then neutralized with 10% Na CO and salted out; after centrifugationand drying, a yellow powder, which dyes cotton in a fast yellow shade,is obtained.

EXAMPLE 8 10 g. of the above-mentioned triazine (XI) are dissolved in 40cc. of acetone and poured into 50 cc. of water and 50 g. of ice. Intothe thus obtained suspension, a solution consisting of 15 g. of isogammaacid (99.4%), dissolved in 350 cc. water and neutralized, and 4.7 g. of

sodium acetate is poured dropwise during 1 hour and under agitation.

The temperature is allowed to reach 20-25 C. and the agitation iscontinued for 5-6 hours. After neutralization the thus obtained solutioncontaining the naphthol is used as such for preparing the followingdyestuff:

SlO Na or: o-o-oH,

A N N m to.

It is obtained by coupling in slightly alkaline medium the diazoniumsalt of the orthanilic acid with the condensation product betweenisogarnma acid and the triazine (XI).

The dyestuff dyes cotton in a very fast orange shade.

EXAMPLE 9 By working as described in Example 8 and using the diazoniumsalt of the Tobias acid, the following dyestutf is obtained; it dyescotton in a very fast orange shade.

'8 EXAMPLE 10 By working as described in Example 8 and using thediazonium salt of the rn-amino-benzoic acid, the following dyestutf:

ON hlo-t i-orra 00011 on t:)

NaOiS NlI-kpyJ-Cl is obtained; it dyes the cellulosic fibers in abrilliant and fast orange shade.

EXAMPLE 11 The triazine dyestulf having the structure:

CHr-l-CH:

SOaNa is obtained by coupling the diazonium salt of the l-amino-2-sulpho-4-acetyl-amino-benzene with the condensation product of thetriazine (XI) with isogamrna acid, in a slightly alkaline medium(pH=8.5). The dyestuff dyes cotton in a fast scarlet shade.

EXAMPLE 12 By working as described in Example 8 and using the diazoniumsalt of the amino G acid the following dyestutf:

SO3N8 is obtained; it dyes cotton in a scarlet fast shade.

EXAMPLE 13 NH IO (31 NaOgS and dyes cotton in a very fast blue shade.

EXAMPLE 14 13.8 g. of

(HOaSh-Ft-SOzNH S0311 NHz.IICl

wherein Ft is a copper phthalocyanine chromogen, are suspended in 200cc. of water and neutralized in order to have a complete solution. Then,2.1 g. of sodium acetate are added and the resulting solution is quicklypoured dropwise into the suspension of 25 cc. of acetone and 25 cc.water of the triazine derivative (XI) (4.6 g.) and cooled with ice.

The whole is heated at 40 C., for 3-4 hours, with agitation. Afterneutralization the whole is salted out and the precipitate is collectedby centrifugation.

The dyestuff has the following structure:

i w-sor-Nn -SOaNa (SOgNaL, N

NE |-o1 1 NC-C-OH:

and dye-s cotton in a very fast turquoise shade.

EXAMPLE 15 Preparation of triazine (XII):

Clix-CH3 l 1 Ol NJCl (XII) 30 g. of cyanuric chloride are dissolved in230 cc. of methylethylketone and to this solution 55 g. of crushed iceare added. The thus obtained suspension is first neutralized with 10%-Na CO and then an aqueous solution of potassium cyanide (10. 6 g. ofKCN; 150 cc. of H 0) is added dropwise at 46 C. over about 50 minutes.

During the KCN dropping the pH of the reaction mass is 9.5-10. When KCNaddition (50 minutes) is finished, the pH of the suspension graduallydecreases and after further 35-45 minutes is 6.5. The suspension isneutralized and diluted with water and ice (220 cc. of H 0, 220 g. ofice) and filtered. The precipitate is thoroughly washed with water andthen dried under vacuum.

The product is crystallized from n-hexane.

Preparation of the amine (XIII) NHg (XIII) 0.1 mol of triazine (XII) isdissolved in 55 cc. of acetone and the solution is poured into 120 cc.of water and 120 g. of ice. Into the thus obtained emulsion is droppedwithin 45 minutes, under stirring, the neutral aqueous solution of 0.1mol of sulphonated m-phenylenediamine (220 cc. of Water), containing 0.1mol of sodium acetate, While the temperature of the reaction mass isallowed to rise spontaneously to 20 C.

When the addition is finished, stirring is continued for further 5-6hours and then the obtained solution is neutralized with %-Na CO Thethus obtained solution is employed as such for the preparation of thefollowing dyestuff:

CH3 oo-onz-ona NaOask/ S O Na EXAMPLE 16 When 1 (4sulpho-phenyl)-3-methyl-5-pyrazolone is used as coupling agent for theamine (XIII), prepared according to the preceding example, a dyestulfhaving the following structure is obtained:

C Ha

l SOaNa which dyes cotton in a yellow shade, very fast to wettreatments.

EXAMPLE 17 By coupling the amine (XIII), prepared according to Example15, with benzoyl-K acid the following dyestutf is obtained:

(l) CHz-CH3 N NaOas S OaNa which dyes cotton in a very fast red shade.

EXAMPLE 18 Employing as coupling agent for the amine prepared accordingto Example 15, 1 (2',5'-dichloro-4-sulphophenyl)-3-metl1yl-5-pyrazolone,the following dyestuif is Obtained, which dyes cellulosic fibers in ayellow shade, fast to washing.

at N

| SOaNa EXAMPLE 19 Starting from the amine (XIII), prepared according toExample 15, working as in the preceding examples and using ureide ofisogamma acid as coupling agent, the following dyestuff is obtained:

NaOzS which dyes cotton in a fast orange shade.

EXAMPLE 20 A dycstutf having the following structure:

i N N N (ll-k J NH -SOsNa on Naoas is obtained from the amine (XIII)analogously to the preceding example, using acetyl isogamma acid ascoupling agent.

Said dyestuff dyes cotton in an orange shade, very fast to wettreatments.

EXAMPLE 21 Preparation of the triazine dyestutf having the structure:

r SOaNa CH: OC--CHz-CH:

\1 CN N=N- NH =K Cl SOaNa 3 g. of the triazine XII are dissolved in 18cc. of acetone and poured into 55 g. of water and ice. An aqueoussolution containing 1.4 g. of sodium acetate and 7.3 g. of the amine:

SlOaNa l N: @N...

dissolved in 280 cc. of water is added dropwise to the suspension, keptunder agitation.

When the addition is completed, the temperature is allowed to rise to20-25 C. and the suspension is stirred till complete solution is reached(4-6 hours); the solution is neutralized with l0%-Na CO and salted out:after centrifugation and drying, a yellow powder is obtained, which dyescotton in a fast yellow shade.

EXAMPLE 22 \NJNHK/ some is employed to prepare the following dyestulf:

Said dyestufi is obtained by coupling in a slightly alkaline medium, thediazonium salt of orthanilic acid with the condensation product ofisogamma acid with the triazine (XII).

It dyes cotton in a very fast orange shade.

EXAMPLE 23 By operating as described in Example 22 and using thediazonium salt of Tobias acid, the following dyestutf is obtained:

CH: NC--CIh-CHa some which dyes cotton in a very fast orange shade.

13 EXAMPLE 24 By operatin-g as described in Example 22 and employing thediazonium salt of m-arnino-benzoic acid, the following dyestutf isobtained:

iiiifhmiji.

which dyes cellulosic fibers in a brilliant orange shade.

EXAMPLE 25 The triazine dyestufi having the structure:

CN HaC--CHg-CH; SO Na OH is obtained by coupling, in a slightly alkalinemedium (pH=8.5), the diazonium salt of 1-amino-2-su1pho-4-acetylaminobenzene with the condensation product of the triazine (XII)with isogamma acid.

It dyes cotton in a fast scarlet shade.

EXAMPLE 26 By operating as described in Example 22, and employing thediazonium salt of amino G acid, the following dyestulf is obtained:

'which dyes cotton in a fast scarlet shade.

EXAMPLE 27 NaOa 3 g. of triazine derivative (XII) are dissolved in 20cc.

31 Naols SON CH3 N IIII V 3 a I Nc-i-ok -NH NH 0 orn- H2 and dyes cottonin a very fast blue shade.

'EXAMPLE 28 13.8 g. of

(HOaSLr-Ft-SOg-NH-Q-SO:

l IHmHCl (wherein Ft is a copper phthalocyanine chromogen) are suspendedin 200 cc. of water and neutralized in order to obtain a completesolution. Then 2.1 g. of sodium acetate are added and the solutionobetained is rapidly added dropwise to the suspension in acetone (25cc.) and water (25 cc.) of the triazine derivative (XII) (4.8 g), cooledwith ice.

The whole is heated to 40 C. for 3-4 hours, keeping it in agitation;after neutralization it is salted out and the precipitate is collectedfor centrifugation.

The dyestufi has the following structure:

Ift-SOz-NH-Q-SOaNrt (S OaNa) n I N T l 0 C Ha-JJ-CHrCHa and dyes cottonin very fast shade.

EXAMPLE 29 2 parts of dyestuff obtained according to any of thepreceding examples from 15 to 28 are dissolved cold in 2000 parts ofwater. The dyeing bath thus obtained is brought to a temperature of 60C., and 100 parts of wetted cotton yarn :are introduced into the bath.

Then two about equal doses of sodium sulphate are added in an amountcorresponding to a concentration of 40 g./l.; the first addition is madeafter 5 minutes, the second after 10 minutes.

Thereafter the temperature of the dyeing bath is lowered to 50 C. in 20minutes, 5-8 g./l. of anhydrous sodium carbonate are added, and thedyeing is continued for 60 minutes.

Now the bath is emptied and the yarn is thoroughly washed first withcold Water, then with boiling water, and finally with a solution ofnon-ionic detergent (1-3 g./l.) for 30 minutes, A particularly stabledyeing in brilliant shades is obtained.

EXAMPLE 30 A 10 g. cotton lea is immersed in a bath consisting of 0.2 g.of the dyestuif prepared according to Example 13 and dissolved in 200ml. of water, and then the temperature is raised up to 60 C. 40 g./l. NaSO are added and the temperature is permitted to drop to 50 C, in 20-30minutes.

At this temperature 8 g./l. Na 'CO preferably in two doses with a10-minute interval, are added and the dyeing is continued for 1 hour.

The cotton lea is rinsed with cold water, then with hot water, and istreated for 30 minutes with a solution containing 2 g. /l. of anon-ionic detergent. Then the material is rinsed many times with coldwater and dried.

The cotton lea is dyed in a blue shade having very good 'fastness to wettreatments and to light.

EXAMPLE 31 A cellulosic fabric is impregnated in a foulard with asolution consisting of 30 g./l. of the dyestuff according to Example 3,15-20 ml./l. o'f'3'6 B. NaOH, 10 g./l. Na SO and the liquid in excess iswrung out so that the dyestulf solution retained in the fabric amountsto only of its weight. The fabric thus impregnated is wound on a rollerand insulated from the room by a polyethylene cover or other insulatingmaterial.

After 3 or 4 hours the roller is unwound and the fabric is washed manytimes in cold water and then in hot water saponified for 30 minutes witha solution containing 2 g./l. of a non-ionic detergent, The cellulosefabric appears dyed with a red shade very fast to wet treatments and tolight.

We claim:

1. The dyestulf having the structure:

NH: O l

('11 NaOaS E N I 4 HO- 0 J-NH --NH 2. The dyestufi having the structure:

NH: (I)

Cl NaOaS 5 A CH9 N CaHs-iO-LN)-NH NE A N 10 SO3N8 References CitedUNITED STATES PATENTS 15 3,065,191 11/1962 Heslop et a1. 2602493,254,084 5/1966 Fleischhauer et al. 260-249 3,313,830 4/1967 Braun eta1. 260249 JOHN D. RANDOLPH, Primary Examiner,

J. M. FORD, Assistant Examiner.

